The reduction of titanocene dichloride Cp2TiCl2 with lanthanide metals has led to the discovery of a surprising lanthanide effect: while with most lanthanides, a divalent [Cp2Ti] equivalent was obtained, the use of samarium or ytterbium only led to the reduction to trivalent [Cp2TiCl]-type complexes, including the structurally characterized heterobimetallic complex [Cp2Ti(μ-Cl)2SmCl2(THF)3]. These results were corroborated by reactivity studies (alkyne coupling and radical reactions), EPR spectroscopy and electrospray mass spectrometry, providing new insights into the reduction chemistry of lanthanide metals.